WO2018083002A1

WO2018083002A1 - Method and device for carrying out endothermic gas phase-solid or gas-solid reactions

Info

Publication number: WO2018083002A1
Application number: PCT/EP2017/077433
Authority: WO
Inventors: Grigorios Kolios; Bernd Zoels; Matthias Kern; Jens Bernnat; Rene Koenig; Friedrich GLENK; Achim WECHSUNG
Original assignee: Basf Se
Priority date: 2016-11-04
Filing date: 2017-10-26
Publication date: 2018-05-11
Also published as: US20200061565A1; US11691115B2; DE112017005572A5; RU2752976C2; RU2019117068A; RU2019117068A3

Abstract

The invention relates to a method for carrying out endothermic gas phase-solid or gas-solid reactions, in which in a production phase in a first reactor zone, the production zone, which is at least partially filled with solid particles, the solid particles being in the form of a fixed bed, a moving bed and in sections/or in the form of a fluidised bed, the endothermic reaction is carried out and the product-containing gas flow is removed from the production zone in the region of the highest temperature level plus or minus 200 K, and the product-containing gas flow is guided through a second reactor zone, the heat return zone, which at least partially contains a fixed bed, the heat of the product-containing gas flow being stored in the fixed bed. In the following purging step, a purge gas is guided in the same flow direction through the production zone and the heat return zone, and in a heating zone, which is arranged between the production zone and the heat return zone, the heat required for the endothermic reaction is introduced into the product-containing gas flow and into the purge flow or into the purge flow. Then, in a regeneration phase, a gas flows through the two reactor zones in the reverse flow direction and heats the production zone. The invention also relates to a structured reactor comprising three zones: a production zone containing solid particles, a heating zone and a heat-return zone containing a fixed bed, the solid particles and the fixed bed consisting of different materials.

Description

SOLID REACTIONS

The present invention relates to a method for carrying out endothermic gas-phase or gas-solid reactions, wherein in a production phase in a first reactor zone, the production zone which is at least partially filled with solid particles, wherein the solid particles in the form of a fixed bed, a moving bed and in sections / or in the form of a fluidized bed, the endothermic reaction is carried out and the product-containing gas stream in the range of the highest temperature level plus or minus 200 K is withdrawn from the production zone and the product-containing gas stream through a second reactor zone, the heat recovery zone, which at least partially contains a fixed bed is passed, wherein the heat of the product-containing gas stream is stored in a fixed bed, and in the subsequent rinsing step, a purge gas is passed in the same flow direction through the production zone and the heat recovery zone, and in a He izzone, which is arranged between the production zone and the heat recirculation zone, the heat required for the endothermic reaction is introduced into the product-containing gas stream and into the purge stream or into the purge stream, and then in a regeneration phase, a gas flows in the reverse flow direction through the two reactor zones and the production zone heats up. Furthermore, the present invention relates to a structured reactor and its use.

Endothermic reactions are often at the beginning of the value chain of the chemical industry, for example in the separation of petroleum fractions, the reforming of natural gas or naphtha, the dehydrogenation of propane, the dehydroaromatization of methane to benzene, the reverse Boudouard reaction, coal gasification or the Pyrolysis of hydrocarbons. In these reactions, temperatures between 500 ° C and 1700 ° C are required to achieve technically and economically interesting yields. The reason for this lies mainly in the thermodynamic limitation of the equilibrium conversion. The provision of the required heat of reaction at this temperature level poses a major technical challenge.

Fluidized bed reactors have been used in the prior art for the heat integrated guidance of endothermic processes (Levenspiel, O. (1988) Chemical Engineering's Grand Ad- perture, Chemical Engineering Science, 43 (7), 1427-1435). For the heat supply of the endothermic reaction, essentially four concepts are used.

It has been proposed in the prior art (see Fluidization Engineering, 2nd Edition, Butterworth-Heinemann, 1991, Daizo Kunii, Octave Levenspiel) to carry out the heat input via circulating particle streams, for example catalyst particles. In this technique, the catalyst particles alternately undergo a production and a regeneration cycle in a circulating fluidized bed. As a result, the particles not only act as a catalyst, but at the same time as a heat carrier to heat the endothermic reaction. In the reaction chamber, the catalyst particles are cooled by the endotherm of the reaction and loaded continuously with eg carbonaceous deposits. To heat and remove the carbonaceous layer, they are treated in the heat recovery zone with a hot regeneration gas. Prerequisite for this technique are, however, resistant to oxygen and mechanical influences resistant particles.

US 2002/0007594 discloses a process for the parallel production of hydrogen and carbonaceous products in which natural gas is introduced into a reaction space and thermally decomposed in the presence of a carbon-rich solid. US 2002/0007594 discloses that in a reactor separate from the reaction space of the thermal decomposition, the carbonaceous solid is heated. The heating takes place by the resulting combustion of hydrocarbons or hydrogen combustion gases. Subsequently, the heated solid is introduced into the reaction space.

The disadvantage of using a solid as a heat transfer medium is that the solid must be heated above the temperature level of the reaction in a separate combustion chamber and circulated between the combustion chamber and the reaction chamber. The handling of the hot solid leads to extreme thermal and mechanical stress on the reactor and the control devices. Furthermore, the solid particle flow is coupled to the heat demand of the reaction and a uniform distribution of the mass flows over the cross section is a necessary condition for achieving the optimal heat integration. Consequently, the ratio between the gas flow and the flow of solids can be adjusted only within a narrow range. In addition, the pyrolysis product stream goes through a region of decreasing temperature where the backreaction can take place. Thus, in this region of the reactor, the back-reaction to the target reaction can take place and reduce the yield of the gaseous target products. For example, in the case of methane pyrolysis, the yield loss may be up to 5%, in the case of steam reforming of methane, up to 50%. The prior art (e.g., U.S. 6,331,283) further discloses autothermal processes in which the heat required for the endothermic reaction is generated via an exothermic co-reaction in the same reaction space. The disadvantage of these autothermal processes is the contamination of the gaseous product stream by the flue gases, e.g. in the case of hydrocarbon pyrolysis, entrainment of C-containing components into the hydrogen-rich product stream. Furthermore, the losses in the product yield are disadvantageous, in the case of hydrocarbon pyrolysis, substantial loss of the pyrolysis carbon. Further, heating the fuel gas for the exothermic accompanying reaction may be detrimental to heat integration.

US 4,240,805 describes a cyclic stream reforming process for hydrogen production in a fixed bed reactor. In the production phase, the educt gas is heated in the reactor zone filled with solid particles 1 and reacted in the zone 2 of the reactor, which is filled with catalyst. The product stream leaves zone 2 at high temperatures and cools in Zone 3, which is filled with inert material. In the regeneration phase, hydrogen and oxygen flow opposite to the product stream separately from each other through the zone 3 and heat up. In zone 2, hydrogen and oxygen are combined so that the combustion reaction heats zones 2 and 1 and the production phase can begin again.

US 2003/0235529 describes the production of synthesis gas in a cyclically operated 2-zone fixed-bed reactor. The first zone of the reactor is filled with catalysts and the second zone is filled with intermaterial. In the production phase, the reaction takes place in the first zone and the hot product stream cools down in the second zone. In the regeneration phase, oxygen and fuel flow through the reactor in the reverse flow direction, which burn at the transition from zone 2 to zone 1 and supply the heat for the next production phase. It is clear in FIG. 2 of US2003 / 0235529 that during reforming (reform, 149) the reaction front (right flank) moves much faster than the pure temperature front (left flank). A disadvantage of the disclosed mode of operation in these non-synchronous temperature fronts is that force is forcibly discharged from the reactor to set the output profile for the next cycle, resulting in increased energy consumption. As illustrated in example 1, the optimum adjustment of the heat capacity flow between the production phase and the regeneration phase of 1: 1 deviated by a factor of 4 in order to achieve an acceptable turnover of the reforming. According to example 1, 82.35% and according to example 2 74.64% of the heat released are used for the reforming.

US 2007/0003478 describes the cyclic production of synthesis gas in a 3-zone fixed bed reactor. Zones 1 and 3 are filled with inert material and zone 2 with catalyst. In production phase 1, the reactant gas is heated in zone 1. Before zone 2, oxygen is supplied, so that sufficient heat is available in zone 2 for the endothermic synthesis gas reaction. Subsequently, the product stream cools down in zone 3. In the production phase 2, educt gas in the zone 3 is heated in the reverse flow direction and oxygen is supplied before the zone 2. In US 2007/0003478 thus no regeneration phase is described. The reaction route and the driving style are symmetrical.

The third concept is based on the fact that the heat is transferred indirectly, for example recuperatively (eg EP 15 16 8206) or via heat pipes (eg US 4,372,377), from the exothermic to the endothermic reaction chamber. A disadvantage of this concept are the complex installations in the hot section of the reaction chamber, the high material and constructive demands on the seal and to avoid thermal stresses. Furthermore, these internals interfere with the solids flow. Another problem with this concept is the fouling of the heat exchanger surfaces; For example, in the case of hydrocarbon pyrolysis, the separation of pyrolytic carbon preferably takes place on hot surfaces. The fourth concept is based on the use of gaseous heat transfer media for the coupling of heat for endothermic decomposition reactions:

WO 2013/004398 discloses that the thermal energy for the heat transfer medium is generated outside the reaction space and the gaseous heat transfer medium is inert to the decomposition reaction and / or is a product of this reaction. The disadvantage is that the solid particle flow is coupled to the requirements of heat integration. Further, the decomposition reaction product stream passes through a region of decreasing temperature in which the backreaction can take place.

US 2,319,679 discloses a process for the pyrolysis of hydrocarbons to acetylene in a regenerative furnace containing a structured packing of silicon carbide bricks. The task of a regenerator is to act as a heat storage for hot exhaust gases of a furnace. This is done by heating one of two refractory-lined channels by hot exhaust gases until it is switched to the second channel when a predetermined temperature is reached. The heated channel now heats the fresh gas. At the same time the other channel is heated again by exhaust gases until a switchover takes place again. The process is cycled with a cycle time of 3 to 5 minutes. In the first phase of the cycle, the regenerative furnace is heated by the exhaust gases of a combustion chamber to temperatures between 1 100 ° C to about 1600 ° C. In the subsequent production phase, cold process gas is passed over the preheated packing and reacted pyrolytically. The pyrolysis gas is introduced immediately after leaving the regenerator in a water bath and quenched to suppress further reaction of the acetylene formed. The process is characterized by the fact that the valves are arranged to control the process in the cold, where they can reliably switch in the required frequency. The disadvantage of this process is the lack of heat integration in the process gas.

US 2,557,143 discloses a process for the pyrolysis of hydrocarbons to "carbon black" and hydrogen in a regenerative furnace The regenerative furnace consists of at least two separate apparatuses, a "reactor" and an "oven." Both apparatuses are filled with random ones Packages of temperature-resistant particles, eg ceramic materials or of carbon The pyrolysis process gas is only in contact with the reactor A second gas stream, eg hydrogen or a gas inert to the pyrolysis reaction, circulates as a heat transfer medium between the reactor and the furnace cyclically operated and comprises four phases:

A hydrocarbon flows through the preheated packing in the reactor and is converted to hydrogen and thermal carbon black (1); A fuel is burned and the heat of combustion is stored in the pack of the furnace (2); A non-oxidizing gas flows through the preheated packing of the furnace (3); the superheated heat transfer stream heats up the packing of the reactor. The pyrolysis produces hydrogen and thermal black ("thermal black"). During the start-up phase, a stationary permanent soot charge builds up in the reactor. In steady-state operation, the produced soot is discharged with the process gas.

The disadvantages of this process are: shut-off valves are required in the hot zone of the process line and the pyrolysis product stream passes through a region of falling temperature in which the reverse reaction can take place.

No. 7,943,808 discloses a cyclic process with periodic flow reversal for acetylene synthesis in a two-zone reactor. The first and second zones of the reactor are designed differently. The cross section in the first zone is split longitudinally into two channels. The cross section of the second zone is homogeneous. In this case, during the first half-cycle, a combustion reaction between the first and the second zone of the reactor heat is generated and stored in the second zone of the reactor. Subsequently, methane is passed through the reactor in the reverse flow direction. In this case, methane is reacted in the preheated second reactor zone to acetylene and rapidly quenched in the first reactor zone. A disadvantage of this method is the complexity of the reactor, due to the structuring of the cross section in the first reactor zone. This reactor design does not allow solids to be fed or removed from the reactor.

The object of the present invention is to overcome the mentioned disadvantages in the prior art, i. to show a process concept for carrying out endothermic gas phase and endothermic gas-solid reactions in which (i) no valves in the hot region of the process section are required, (ii) a mode of operation with integrated heat exchange is possible without the solid particle flow to the requirements of Heat integration and / or the general heat demand is coupled, (iii) an operating mode is selected which leads to setting a ratio of the heat capacity flows between the production phase and the regeneration phase close to 1: 1 and enables synchronous temperature fronts via this, (iv) a back reaction of the gas -Feststoffreaktion in the gaseous product stream is excluded as much as possible to avoid soot formation in the product stream and thus cleaning steps, (v) no handling of hot solid is needed, and / or (vi) no contamination by autothermal heating, is used. The focus is on tasks (ii) and (iii).

Description of the invention

The object is achieved by a method for carrying out endothermic gas-phase or endothermic gas-solid reactions, which is characterized in that in a production phase in a first reactor zone, the production zone which is at least partially filled with solid particles, wherein the solid particles in the form a fixed bed, a moving bed and sections / or in the form of a fluidized bed, the endothermic reaction is carried out and the product-containing gas stream in the range of the highest temperature level plus or minus 200 K is withdrawn from the production zone and the product-containing gas stream through a second Reactor zone, the heat recovery zone, which at least partially contains a fixed bed, is passed, wherein the heat of the product-containing gas stream in the Fixed bed is stored, and in the subsequent rinsing step, a purge gas is passed in the same flow direction through the production zone and the heat recovery zone, and in a heating zone, which is arranged between the production zone and the heat recovery zone, the heat required for the endothermic reaction in the product-containing gas stream and in the flushing stream or is introduced into the purge stream, and then in a regeneration phase, a gas flows in the reverse flow direction through the two reactor zones and heats the production zone.

The term "highest temperature level" is understood to mean the highest temperature reached in the respective endothermic reaction, preferably in the highest temperature level plus or minus 150 K, preferably plus or minus 100 K, in particular or minus 50 K.

The object is achieved in particular by a method for carrying out endothermic reactions, comprising the method steps (a) introducing an educt-containing gas into a preheated production zone and carrying out the endothermic reaction in the production zone which is at least partially filled with solid particles (process step: production) , (b) optionally heat input to the product-containing gas stream in a heating zone located downstream of the production zone (process step: heat input), (c) heat transfer from the product-containing stream from step (b) to a fixed bed including in particular materials suitable for the Target reaction are inert and are not products of the target reaction, in a heat recovery zone, which is located downstream of the heating zone (process step: heat storage), (d) purging the production zone and the heat recovery zone with an inert purge gas in the flow direction of the edukthaltigen gas (process step Sp (e) heat input to the product-containing gas stream in a heating zone, which is arranged downstream of the production zone (process step: heat input), (f) interrupting the introduction of edukthaltigem gas and introducing a regeneration gas in the heat recovery zone with compared to edukthaltigen gas opposite flow direction , (g) heat transfer from the solid particles heated in step (c) and / or structured internals to the regeneration gas (process step: heat release), (h) heat transfer from the regeneration gas heated in step (g) to the solid particles in the production zone ( Process step: heating), (i) interrupting the introduction of regeneration gas into the heat recovery zone and introducing a educt-containing gas into a preheated production zone with compared to the regeneration gas flow direction analogous step (a).

The object is further achieved by a structured reactor comprising three zones, a production zone comprising a packing of solid particles, a heating zone and a heat recovery zone containing a fixed bed, eg packings of solid particles and / or shaped bodies of structured regenerator internals such as monoliths or plates (see "Regular Catalyst form body for industrial syntheses "by Eigenberger et al., VDI, Research Reports, 1993, Series 14, No. 1 12), wherein the pack of solid particles and the fixed bed made of different materials and solid particles can be filled during the reactor operation and ausschleusbar.

The solid packing in the production zone is also referred to below as the "production bed." The production bed is advantageously formed of randomly arranged particles which can be reactive, catalytically active or inert.The fixed bed of the production zone is advantageously a catalyst for an endothermic A gas phase reaction, a solid contact for an endothermic gas-solid reaction or the product of an endothermic reaction The fixed bed in the heat recovery zone is also referred to below as the "regenerator bed". The regenerator bed may advantageously consist of randomly arranged particles and / or a structured packing of fixed installations. The materials of the regenerator bed can be inert and are advantageously not products of the target reaction. The process according to the invention or the reactor according to the invention is advantageously used in a gas-solid reaction.

The process according to the invention or the reactor according to the invention is advantageously used in pyrolysis, steam cracking, dehydrogenation, dehydroaromatization, reforming, Boudouard reaction, alkane-amine dehydrogenation and / or water thermolysis.

The CO 2 emission in the process according to the invention for 100 kg of hydrogen is advantageously less than 10 kg CO 2 / kgH 2, preferably less than 8 kg CO 2 / kgH 2, in particular less than 6 kg CO 2 / kgH 2, in particular less than 4 kg CO 2 / kgH 2, especially at less than 2 kg CO 2 / kgH 2, most preferably the inventive method is C02 emission-free.

The term "production" is understood to mean the introduction of an educt-containing gas into the preheated solids packing in the production zone and its conversion.

The term "heat input" means the introduction of an oxygen-rich gas into the heating zone and the combustion of a fuel gas contained either in the main stream from the production zone during the production step or during the purge step, this fuel gas being heated to temperatures of 350 by the heat stored in the production bed ° C to 1200 ° C, preferably from 400 ° C to 1000 ° C. Alternatively, the fuel gas can be introduced with a side stream directly into the heating zone.

The term "storage" is understood as meaning the throughflow of the regenerator bed and the transfer of the sensible heat contained in the gas stream to the regenerator bed. The term "release" is understood to mean the introduction of a regeneration gas into the preheated regenerator bed in the opposite direction to the gas flows during the production phase and the absorption of the sensible heat stored in the regenerator bed.

The term "heating" is understood to mean the flow through the production bed with the regeneration gases from the regenerator bed during the release and the transfer of the sensible heat contained in the regeneration gas to the packing of the production bed.

The term "purging" is understood to mean the introduction, in the same direction to the gas streams during the production phase, of an inert, for example nitrogen-rich, or exothermically reacting, for example hydrogen-rich, gas in the partially cooled production bed.

The term "holding" is understood to mean the interruption of the flow through the production bed and / or the regenerator bed.

The term "idle" refers to the step in the heating zone during which the product gas or regeneration gas does not absorb heat within the heating zone.

The term "discharge" is understood to mean the exchange of the gas content of the entire reactor, thus advantageously avoiding contamination of the process gases in the individual steps.

The term "filling" refers to the introduction of a stream of solids at the top of the production bed This step may occur simultaneously with the emptying of a portion of the production bed from the bottom of the production zone.

Advantageously, the process according to the invention is operated cyclically. Each cycle comprising steps a) to g) is advantageously 2 minutes to 24 hours, preferably 5 minutes to 12 hours, particularly preferably 10 minutes to 10 hours, in particular 30 minutes to 5 hours.

A cycle comprises at least two phases, the production phase comprising steps (a) to (c), ie production in the production zone, additional heat input in the heating zone and storage of the heat in the heat recovery zone, and the regeneration phase, steps (d) to (g), ie heat release from the heat transfer zone and heating of the production zone. A cycle may also advantageously comprise the following further steps: holding, rinsing, removal of the solid product and / or filling of solid particles. These further steps may be included in each cycle, but may be missing over several cycles. Furthermore, the step of the trigger can extend over several cycles, possibly continuously. The frequency of removal of the solid product can be interpreted on the basis of process-specific criteria. The following table lists criteria for different processes: Process Criterion for the emptying / replacement of solid particles in the production zone

Pyrolysis Mass increase of the vehicle

Dehydration accumulation of coke

Irreversible deactivation

abrasion

Dehydroaromatization accumulation of coke

Irreversible deactivation

abrasion

Steam splitting accumulation of coke

Irreversible deactivation

Reverse Boudouard Reak Mass Decay of Solid Reactant Coke

tion

Deacon mass removal of the active solid "leaching"

Water thermolysis Irreversible deactivation

abrasion

NH3 cleavage Irreversible deactivation

Advantageously, two or more steps may take place synchronously in time. For example, For example, the steps of extracting and filling solid particles can be synchronized. Furthermore, the steps rinsing, drawing off and / or filling of solid particles can take place synchronously.

It is also a continuous filling and / or a continuous withdrawal of solid particles possible. In this case, the steps "Deduction" and / or "Discharge" run in sync with all other steps. The relative duration of the individual process steps that take place in the production zone, based on the duration of an entire period, lie in the following areas:

The production phase advantageously occupies between 10 and 80%, preferably between 20 and 60% of the period. The rinsing step in the production phase advantageously takes place between 0 and 50%, preferably between 10 and 40%, in particular between 30 and 40%, of the period of the period. The regeneration phase advantageously occupies between 10 and 80%, preferably between 20 and 60% of the period duration; if there is a rinse step, the regeneration phase advantageously takes 30 to 40% of the period.

The duration of the steps in the heating zone and in the heat recovery zone is advantageously synchronized with the duration of the steps in the production zone. If no rinsing step is provided in the cycle, the heat input in the heating zone takes place during the production step (see FIG. 3). Otherwise, alternatively or additionally, the heat input in the heating zone takes place simultaneously with the rinsing step in the production zone (see FIG. 4 and FIG. 5), preferably alternatively. The storage step in the heat recovery zone advantageously takes as long as the production step and the rinsing step together. The relative duration of the individual process steps depends advantageously on how many of the reactors according to the invention are connected together to form a system. With the goal of quasi-continuous production, the following rule results:

The intended operating state is advantageously the cyclically stationary or periodic state. This condition is asymptotic in trouble-free operation and is characterized in that the operating conditions of the reactor are equal at time intervals corresponding to the cycle period.

The production phase:

The production phase according to the invention comprises at least three steps in the flow direction of the educt gas: (a) "production", (b) "heat input", and (c) "storage" in the heat return zone.

Step production:

In production step (a), the educt-containing stream in the production zone is advantageously passed through a preheated packing of temperature-resistant solid particles and reacted. The educt-containing stream is advantageously a hydrocarbon-containing gas or vapor, i. a gaseous phase of a substance in equilibrium with the liquid phase. Preference is given to natural gas H, natural gas L, refinery fractions such as liquefied gases (propane, butane), or naphtha, coupling gases and biogas, as described, for example, in WO 2014/095661 or mixtures thereof. A preferred mixture includes natural gas and LPG.

Alternatively, the educt-containing stream is a carbon monoxide-containing, a hydrous, a hydrogen-containing, an HCl-containing and / or a (bio) ethanol-containing gas or vapor. If desired, these starting materials can be mixed with hydrocarbons. By way of example, the following reactions are summarized in tabular form:

The process according to the invention is particularly preferably used in the production of hydrogen, of synthesis gas, of styrene, propene, butene and / or benzene, of acetylene, of carbon monoxide, of hydrogen cyanide and in the calcination of aluminum hydroxide. The following processes are preferred: steam and dry reforming, the thermolysis of water, the dehydrogenation of ethylbenzene to styrene, of propane to propene, of butane to butene and / or of cyclohexane to benzene, the pyrolysis of hydrocarbons, in particular the pyroysis of methane , Ethane, propane and / or butane, as well as the pyrolytic acetylene production, the dehydroaromatization of methane to propane, the ammondehydrogenation of methane to propane, the Boudouard reaction, the calcination (decomposition of hydroxides and carbonates).

The feed temperature of the educt-containing stream is advantageously from -150 ° C to 750 ° C, preferably from -75 ° C to 600 ° C, more preferably from 4 ° C to 400 ° C, in particular from 20 ° C to

250 ° C. The advantage of the low temperatures is that the gas from a kyrogenen purification stage can be used directly and / or the product gas can be fed directly into a cryogenic purification stage, with only a slight drop in temperature for Fractionation is required. Advantages of the higher temperatures are that high boilers can not condense out and the reactor volume can be used completely for the reaction. The preheat temperature is the target value at which the production bed is advantageously heated prior to each production step in the cyclically stationary state. Advantageously, a predominant part of the production bed is heated to this preheating temperature, advantageously between 30% and 100% of the bed, preferably between 40% and 100%, more preferably between 50% and 100%, in particular between 60% and 100% of the bed.

For the preferred variants of the method according to the invention, the value ranges of the preheat temperatures are summarized in tabular form:

In the pyrolysis of hydrocarbons, the production bed is advantageously at 900 to

2000 ° C, preferably preheated to 1 100 to 1900 ° C, more preferably to 1300 to 1800 ° C and in particular to 1400 to 1700 ° C (preheating temperature).

The difference between the feed temperature of the educt-containing stream and the temperature of the preheated solid packing in the reaction zone is advantageously 500 to 2000K, preferably 700 to 1900K, more preferably 900 to 1800K, especially 1000 to 1700K. The onset temperature is the temperature above which the endothermic reaction proceeds at technically relevant reaction rates. For the preferred variants of the method according to the invention, the value ranges of the onset temperatures are summarized in tabular form:

The educt-containing stream advantageously has a flow velocity in the production zone of 0.001 to 20 m / s, preferably from 0.01 to 10 m / s, more preferably from 0.05 to 5 m / s, in particular from 0.1 to 2 m / s. The term "flow velocity" means the empty tube velocity under standard conditions, meaning that the material load of the reaction zone is defined independently of the variation of the operating parameters (pressure, temperature).

Advantageously, the product-containing stream on exiting the production zone to an absolute pressure of 0.1 to 100 bar, preferably from 0.3 to 80 bar, more preferably from 1 to 60 bar, in particular from 3 to 40 bar.

Advantageously, the average residence time of the educt-containing gas stream in the region of the production zone which has the preheating temperature is 0.1 to 900 s, preferably 0.2 to 300 s, more preferably 0.5 to 60 s, in particular 1 to 30 s. In analogy to the flow rate, the residence time in the production bed is meant as the quotient of the void volume of the production zone and the volume flow of the educt-containing gas stream under standard conditions.

For example, the space-time yield of hydrogen production in natural gas pyrolysis is 10 to 10,000 kg H ₂ / h / m ³ , preferably 100 to 1000 kg H ₂ / h / m ³ . The production bed is advantageously a packed bed, ie a packed packing of solid particles. Alternatively, additional fixed installations in the production zone can also be provided, for example in the form of heating elements or in the form of a stationary, regular package. The production bed in this case consists of a mobile and a stationary part.

The solid particles of the production bed are advantageously temperature-resistant in the range from 1000 to 2800 ° C., preferably from 1300 to 2800 ° C., more preferably from 1500 to 2800 ° C., in particular from 1600 to 2800 ° C.

As temperature-resistant solids are advantageously used e.g. ceramic carrier particles, in particular materials according to DIN EN 60 672-3, such as e.g. Alkali aluminum silicates, magnesium silicates, titanates, alkaline earth aluminum silicates, aluminum and magnesium silicates, mullite, alumina, magnesium oxide and / or zirconium oxide into consideration. Furthermore, non-standard high-performance ceramic materials such as e.g. Quartz glass, silicon carbide, boron carbide and / or nitrides serve as temperature-resistant solids.

Furthermore, the use of carbonaceous material as granules is advantageous. In the present invention, a carbonaceous granulate is to be understood as meaning a material which advantageously consists of solid grains which are at least 50% by weight, preferably at least 80% by weight, more preferably at least 90% by weight of carbon, more preferably at least 95 wt .-%, in particular at least 98 wt .-% carbon. The carbonaceous granules advantageously have a grain size, i. an equivalent diameter, which can be determined by sieving with a certain mesh size, of 0.05 to 100 mm, preferably 0.1 to 10 mm, more preferably 0.2 to 5 mm, in particular 0.3 to 3 mm.

Advantageously, the density of the carbonaceous material is 0.15 to 2.25 g / ml, preferably 0.3 to 2 g / ml, more preferably 0.65 to 1.85 g / ml, especially 0.9 to 1.7 g / ml.

Advantageously, the porosity of the carbonaceous material is 0 to 0.95 ml / ml, preferably 0.1 to 0.85 ml / ml, more preferably 0.15 to 0.7 ml / ml, in particular 0.25 to 0.6 ml / ml.

Advantageously, the carbonaceous material has a macroporosity. The average pore radius is advantageously from 0.01 to 50 μm, preferably from 0.1 to 20 μm, in particular from 0.5 to 5 μm. The specific surface area is advantageously from 0.02 to 100 m ² / g, preferably from 0.05 to 10 m ² / g, in particular from 0.2 to 2 m ² / g.

The carbonaceous granules are advantageously spherical. In the method according to the invention, a multiplicity of different carbonaceous granules can be used. For example, such granules may consist predominantly of coal, coke, coke breeze and / or mixtures thereof. Further, the carbonaceous granules 0 to 15 wt .-% based on the total mass of the granules, preferably 0 to 5 wt .-%, metal, metal oxide and / or ceramic. By "coke" in the present invention is meant a high carbon porous fuel (C-mass fraction> 85%).

The ceramic carrier particles advantageously have an unporous and smooth surface, defined by the roughness, or by the type of surface treatment, for example

^* Brevier Technical Ceramics 10.5.4.4

In the case of the ceramic supports, it is advantageous if the pyrocarbon can be "easily" removed from the surface, and polished carrier particles of corundum, stoneware or quartz glass are advantageous.

Advantageously, the rate of descent of the solids flow in the production zone, averaged over a period, is in the range from 0 m / h to 50 m / h, preferably 0 m / h to 10 m / h, in particular 0 m / h to 5 m / h. In particular, the solids flow may correspond to the production rate plus or minus 10% of the solid product, so that the hold-up of the production zone remains constant.

Advantageously, the loading and unloading takes place in the production zone with solid particles, while the production zone is not flowed through with edukthaltigem gas, preferably is not flowed through with a reacting gas, especially during the production zone is traversed by any gas.

The solid packing in the production zone may have different fluidization states during the production step: advantageously a fixed bed, a moving bed or a fluidized bed. The fluidization state may be homogeneous or inhomogeneous over the height of the production zone. In particular, the production zone can be divided vertically into zones with different fluidization states: for example, in the lower section of the production zone a fixed bed or moving bed and in the upper section of the product outlet a fluidized bed or moving bed.

The intimate contact between the gaseous reaction mixture and the solid in the production zone and in the heat recovery zone results from the specific interface between the solid packing and the gas phase, which is greater than 50 m ² / m ³ , preferably greater than 100 m ² / m ³ , particularly preferably greater than 500 m ² / m ³ . It causes an intensive heat exchange with a heat transfer coefficient of advantageously greater than 10 W / m ² / K, preferably greater than 50 W / m ² / K, particularly preferably greater than 100 W / m ² / K between the gaseous reaction mixture and the solid.

The process according to the invention is preferably carried out for the pyrolysis of hydrocarbons without the use of an active metal-containing catalyst.

Alternatively, the solid particles of the production bed can also contain catalysts or the solid bed can consist exclusively of catalysts, so that the production bed is advantageously a catalyst bed. Advantageous catalysts are known to those skilled in the above-mentioned reactions, for example, zeolite-containing catalysts for dehydro-aromatization, Ni-containing catalysts for reforming, Pt-, Fe- or Cr-containing catalysts for dehydrogenation.

Alternatively, the fixed bed may contain a solid, reactive component that is reversibly reacted in a forward and reverse reaction within one cycle. For example, ferrites can be used for the thermolysis of water in this way (Solar Energy, 81 (5), 623-628, 2007). Furthermore, for example, Al (OH) ₃ can be calcined to Al ₂ O ₃ or CaCOs to CaO. In the pyrolysis of hydrocarbons, the target products of this reaction are hydrogen and carbon. The hydrogen advantageously flows through the packing of solid particles, while the carbon is largely deposited on the solid particles. The degree of separation of the carbon on the solid particles is advantageously in the range from 85 to 100%, preferably 90 to 100%, particularly preferably 95 to 100%, in particular 99 to 100%.

Step rinse:

For the rinsing step, the gas composition in the feed of the production zone is advantageously switched over from the educt-containing stream of the production step to a purge gas. The purge gas may have different compositions. For example, the purge gas contains hydrogen, carbon monoxide, carbon dioxide, water vapor, nitrogen, argon or a mixture of these gases. The gas stream used during the purge step may be imported or a recycle stream from the process. Advantageously, the heat input in the heating zone takes place at the same time as the rinsing step in the production zone (see FIG. 4 and FIG. 5). Otherwise, if no rinsing step is provided in the cycle, the heat input advantageously takes place in the heating zone during the production step (FIG. 3 and FIG. 6). The storage step in the heat recovery zone advantageously takes as long as the production step and the rinsing step together. The inlet temperature of the gas stream into the production bed during the rinsing step is advantageously -150 to 750 ° C, preferably -75 to 600 ° C, more preferably 4 to 400 ° C, especially 20 to 250 ° C. This is analogous to the inlet temperature for the educt-containing gas and the regeneration gas.

During the purging step, the gas stream advantageously has a flow rate in the production zone of 0.001 to 20 m / s, preferably from 0.01 to 10 m / s, more preferably from 0.05 to 5 m / s, in particular from 0.1 to 2 m / s up. The ratio between the heat capacity of the gas fed into the reactor during the purging step and the heat capacity of the educt-containing gas in the feed of the production zone during the production step is between 0 and 400%, preferably between 0 and 200%. As a guide, the heat capacity of the gas stream in each step is determined according to the following relationship:

c _p f) [j - ^ -]: Specific heat capacity of the gas with the feed composition at a mean temperature between the feed temperature and the preheat temperature.

Ati i ^s V- Duration of the step i

The run variable i can assume the following meaning: "production", "rinse", "store", "release".

The relative duration of the rinsing step, based on the duration of a full period, is advantageously between 0 and 50%, preferably between 10% and 40%.

Using an inert purge gas, a combustion gas and an oxidizing agent are advantageously fed into the heating zone, so that the heat of combustion raises the mixture temperature at the outlet of the heating zone to the desired preheating temperature.

When hydrogen is used as the fuel, the produced water can advantageously be condensed out and the nitrogen recycled as recycle gas.

The solids packing in the production zone may have different fluidization states during the rinsing step analogously to the production step: advantageously a fixed bed, a moving bed or a fluidized bed, in particular a fixed bed. Step heat input:

In step (b), heat is supplied to the product-containing gas stream leaving the production zone, in particular hydrogen-containing gas stream, thereby increasing the thermal energy of the gas stream. An increase in the thermal energy can be achieved by raising the gas temperature to the level of the required preheat temperature and / or by increasing the amount of gas at the level of the required preheat temperature. The first effect is advantageously achieved by partial combustion of the combustible constituents of the product gas in the heating zone. The second effect is achieved by introducing the flue gases from an external combustion chamber as gaseous heat transfer medium into the heating zone (hot gas feed). Advantageously, the increase of the thermal energy is achieved by raising the gas temperature to the level of the required preheating temperature.

Advantageously, the steps "production" and "heating" run synchronously. The steps "rinsing" and "heating" preferably run synchronously.

The heating zone may be a mixing chamber. The walls of the heating zone can be lined with a temperature-resistant, chemically resistant, inert and heat-insulating layer. The heating zone may contain separate feed lines for side streams such as fuel gas / oxidant-containing gas and / or a gaseous heat transfer medium. The heating zone may contain baffles / baffles for guiding the streams (static mixers) and / or for feeding and distributing side streams. In addition, the heating zone may include a device for igniting a combustible mixture.

The temperature of the gas stream leaving the heating zone is regulated to the predetermined value of the preheating temperature.

The heat input can take place according to all methods known to the person skilled in the art:

For example, in the heating zone, the gas stream containing flammable components leaving the production zone is treated with an oxidant-containing, e.g. oxygenates,

Gas stream, which is fed via separate feed lines in the heating zone, mixed and partially burned. The product-containing gas stream is preheated by the heat stored in the production bed to temperatures of 350 ° C to 1200 ° C, preferably from 400 ° C to 1000 ° C. For example, a heat input can take place in that advantageously a low-cost fuel gas, eg natural gas, an inexpensive liquid fuel, eg naphtha and / or a cost solid fuel, eg injection coal is burned in an external combustion chamber and introduced the hot flue gas via separate supply lines in the heating zone becomes. Alternatively, the fuel and the oxidant can be introduced via separate feed lines in the heating zone and burned there. For example, a heat input by blowing of coal dust carried out at high temperatures of advantageously 1200 to 2200 ° C, preferably 1400 to 2100 ° C, more preferably 1500 to 2000 ° C, especially 1600 to 1900 ° C, and stoichiometric excess primarily to CO is implemented. In this case, the product gas may contain significant amounts of COx. For certain applications, this proportion can be processed specifically as synthesis gas.

Furthermore, the heat input can be effected by feeding in a superheated inert gas, for example nitrogen. The superheated inert gas may e.g. previously heated in a plasma torch or such a plasma torch can be integrated into the heating zone.

Alternatively, a heat input by indirect heating can take place. The product-containing gas stream and the fuel gas, for example an air / natural gas mixture can advantageously be passed through adjacent channels. The heat of combustion is transferred through the duct wall to the process gas. This variant has the advantage that the product gas can be obtained undiluted.

A special form of indirect heating is electrical resistance heating. According to the invention, the electrical heating elements are in thermal contact with the gas stream. Advantageously, the resistive elements are embedded in a heap of temperature-resistant particles, which is flowed through by the product gas.

Alternatively, advantageously, the electrical heating elements may be embedded in a wall that is in thermal contact with the gas stream. Preferably, however, the heat for the endothermic reaction is introduced using the direct input of energy into the product-containing gas stream or into a purge stream.

For example, the product gas stream entering the heating zone is overheated by a temperature difference of from 0 K to 2000 K, preferably from 0 K to 1000 K.

The oxygen-containing gas is for example air or enriched air, wherein the oxygen content of the oxygen-containing gas is advantageously between 20 and 100%, preferably between 40 and 100%, particularly preferably between 50 and 100%, in particular between 60 and 100%. Very particular preference is given to oxygen of technical purity (advantageously greater than 95% by volume oxygen, preferably greater than 99% oxygen, particularly preferably greater than 99.5% oxygen).

It is advantageous to ensure that no ignitable mixture is formed in the feed lines of the side feed to the heating zone. This is ensured, for example, by the fact that the feeders of the side feed, which carry the oxidant-containing gas stream to the heating zone, are defined before the start of the heat-input step and at the end of the heat-input step. be rinsed with pure nitrogen, argon, C02, H20 vapor or mixtures of these gases. The volume of gas delivered through the conduits during this intermittent inertisation cycle is five to fifty times the volume of the conduit. Alternatively, nitrogen, argon, CO 2, H 2 O vapor or mixtures of these gases can be fed permanently into the feeders of the side feed.

The inlet temperature of the oxidant-containing gas stream is advantageously between room temperature and 1500 ° C., preferably between 150 and 1100 ° C., more preferably between 300 and 900 ° C., in particular between 400 and 650 ° C.

During the heat input step, the volume flow ratio of oxygen stream to product-containing gas stream is advantageously between 0.004 and 0.16, preferably between 0.008 and 0.12, more preferably between 0.012 and 0.08, in particular between 0.016 and 0.04.

Alternatively to oxygen, other oxidizing agents may also be used, e.g. NO or N20 can be used.

The mixing temperature of the gas flow at the outlet of the heating zone corresponds to the required preheating temperature. The deviation from the nominal value is between -200 and + 200K, preferably between -100 and + 100K, more preferably between -50K and + 50K.

The ratio between the heat capacity of the gas fed in via the side feed and the heat capacity of the educt-containing gas in the feed of the production zone is between 0 and 5, preferably between 0 and 1, particularly preferably between 0 and 0.5, very particularly preferably between 0 and 0, 1 .

As a guide, the heat capacity of the gas flow in each zone is advantageously determined according to the following relationship:

at a

average temperature between the inlet temperature and the preheating temperature.

Ati i ^s V- Duration of the step i

The running variable i can assume the following meaning: "production zone", "heat recovery zone".

During the heat input step, the heat output related to the volume of the heating zone is 0, 1 MW / m ³ to 50 MW / m ³ , preferably from 0.5 MW / m ³ to 20 MW / m ³ , in particular from 1 MW / m ³ to 10 MW / m ³ . For example, the heat input is distributed to one or more heating zones installed along the heat recovery zone. This variant is shown in FIG. The number of page feeds is advantageously determined according to the following rule:

_ninj = 1 + int (^ a_ ^■ \ AT _ad |), where

n _inj : number of page _feeds

int: function: integer part of a real number

X At the required preheating temperature achievable equilibrium conversion of the educt during the production phase.

ΔΤ _β [K]: effective temperature elevation within the reaction zone. AT _eff corresponds to the difference between the required preheat temperature and the onset temperature of the endothermic reaction. \ ΔΤ _αά \ [K]: absolute value of the adiabatic temperature change of the endothermic reaction (for definition see http://elib.uni-stuttgart.de/bitstream/1 1682/2350/1 / docu_FU, pdf page 31).

Determining the position of the feeds is governed by a length scale, which can be clearly described as the "migration interval of a thermal front"

c _fxb ^ _j ^ -]: specific heat capacity of the solid _packing in the heat recovery zone.

At [s] -. Duration of the relevant time interval (as a rule, duration of the storage step within the cycle).

The positions of the side inlets are advantageously determined according to the following rules: (i) the distance of the first side feed from the beginning of the regenerator bed in the flow direction during the production phase corresponds favorably to the thermal front migration interval during the production phase, (ii) the distance between successive side feeds advantageous to the migration interval of the thermal front during the production phase.

This variant is particularly preferred if no rinsing step is provided in the cycle. Compared with the arrangement of the heating zone between the production zone and the heat recovery zone, a smaller side stream is required to transfer the heat for the storage step.

Step "storage"

The product-containing gas stream is passed in step (c) in the heat recovery zone via a fixed bed, for example a packing of solid particles and / or structured regenerator internals. The gas stream is advantageously cooled and the heat stored in the solid packing. Advantageously, a portion of the regenerator bed is heated to the required preheat temperature for the production step, advantageously from 10% to 100% of the bed, preferably from 30% to 100%, more preferably from 40% to 100%, especially from 50% to 100% of the bed.

The heat transfer resistance during heat exchange between the gas and the fixed bed in the regenerator bed advantageously has a length of the transfer units or height-of-transfer units (HTU) of 0.01 to 5 m, preferably 0.02 to 3 m, particularly preferably 0.05 up to 2 m, in particular from 0.1 to 1 m. The definition of HTU is taken from http: //elib.uni- stuttgart.de/bitstream/1 1682/2350/1 / docu_FU. pdf page 74.

The exit temperature of the product-containing storm from the regenerator bed varies with time within the storage step. Typically, in the first half of the storage step, the exit temperature increase is less than 20%, preferably less than 10%, more preferably less than 5%, based on the difference between the preheat temperature and the start temperature at the exit of the heat transfer zone at the beginning of the storage step.

In the second half of the storage step, the outlet temperature rises continuously. The difference between the exit temperature at the end and at the beginning of the storage step is between 1% and 100%, preferably between 10% and 70%, more preferably between 20% and 50% of the difference between the preheat temperature and the initial temperature at the exit of the heat transfer zone at the beginning the storage step.

Advantageous solid particles for the regenerator bed are packages of materials which are chemically inert with respect to the reverse reaction of the particular endothermic reaction, e.g. ceramic material. As ceramic materials are advantageous: ceramic materials according to DIN EN 60 672-3, in particular alkali aluminum silicates, magnesium silicates, titanates, alkaline earth aluminum silicates, aluminum and magnesium silicates, mullite, alumina, magnesia and / or zirconia and non-standard high performance ceramic materials, in particular Quartz glass, silicon carbide, boron carbide.

Advantageous packing forms for the regenerator bed are (i) random packing of shaped articles, eg balls, cylinders, rings, saddles etc., (ii) structured packing of monoliths, eg honeycomb bodies, refractory bricks, (iii) structured packing of profiled plate packs ("Ha In step (c), the yield losses of the gaseous product of gas-solid reactions, for example of the hydrogen from the pyrolysis of hydrocarbons, are advantageously less than 10%, less than 5%, in particular less than 0 , 5% This advantageous property results from the separation between the gaseous and the solid reaction product at the highest temperature level in the production zone Thus, during the cooling in a chemically inert ceramic packing, the reaction partner for the reverse reaction is absent. Advantageously, the storage step takes place synchronously with the steps of "production" and / or "rinsing" in the production zone and with the step "heat input" in the heating zone If no rinsing step is provided in the cycle, the heat input in the heating zone advantageously takes place during the production step Otherwise, the heat input advantageously takes place in the heating zone at the same time as the rinsing step in the production zone (see Figure 4 and Figure 5.) The storage step in the heat recovery zone advantageously takes as long as the production step and Rinse step together.

The ratio between the heat capacity of the gas passed through the retort bed during the storage step and the sum of the heat capacities of the gases introduced into the production bed and into the heating zone during the production step and optionally during the purge step is between 0.5 and 2, preferably between 0.8 and 1.2.

The regeneration phase:

In the regeneration phase of the feed is advantageously switched from edukthaltigem gas in the production zone to a regeneration gas in the heat recovery zone. The regeneration gas is advantageously passed through the reactor in the opposite direction to the educt-containing and product-containing stream, in particular hydrocarbon stream.

This regeneration gas is e.g. an inert gas and / or a gaseous product of the reaction from step a) and / or a gas mixture from the further process chain / process environment (see example), for example - in the case of methane pyrolysis - the purge gas of pressure swing adsorption for hydrogen purification. The regeneration gas used is preferably nitrogen, hydrogen, carbon monoxide, carbon dioxide, water vapor and / or argon or a mixture of these components.

During the regeneration phase essentially two steps take place: (i) the release of heat in the regenerator bed and (ii) the heating of the production bed.

Release:

The regeneration gas advantageously absorbs heat in the heat recovery zone. The regeneration gas advantageously has an inlet temperature in the heat recovery zone, advantageously from -150 ° C to 750 ° C, preferably from -75 ° C to 600 ° C, more preferably from 4 ° C to 400 ° C, in particular from 20 ° C to 250 ° C on. The inlet temperature is as close as possible to the ambient temperature, i. in the temperature range between -20 ° C and 150 ° C. This is analogous to the inlet temperature for the educt-containing gas.

The gas flow of the regeneration gas advantageously has a flow rate of 0.001 to 20 m / s, preferably from 0.01 to 10 m / s, more preferably from 0.05 to 5 m / s, in particular from 0.1 to 2 m / s , The regeneration gas advantageously has an exit temperature from the heat recovery zone of 900 to 2000 ° C, preferably from 1100 to 1900 ° C, more preferably from 1300 to 1800 ° C, in particular from 1400 to 1700 ° C. The regeneration gas is passed from the heat recovery zone via the heating zone into the production zone. In the regeneration phase, a possible heat input in the heating zone with a heat output related to the volume of the heating zone is advantageously less than 100kW / m ³ . Preferably, the heating zone during the regeneration phase is idle, ie inactive; There is advantageously no heat input.

Alternatively, during the regeneration phase, an oxidant-containing gas and a fuel gas, e.g. Natural gas or a high-energy purge gas, are introduced into the heating zone. The combustion can advantageously raise the temperature of the regeneration gas by 0 to 800K, preferably 0 to 500K, more preferably 0 to 300K, in particular 0 to 100K.

The ratio between the heat capacity of the gas supplied to the regenerator bed during the heat release and the gas supplied to the regenerator bed during heat storage is between 0.5 and 2, preferably between 0.8 and 1.2.

Warm up:

During the regeneration phase, heat exchange between the regeneration gas and the solid particles in the production bed advantageously takes place in the production zone. In this case, the gas flow of the regeneration gas is advantageously cooled and the heat stored in the solid particles. This advantageously provides for the subsequent production phase, i. set the production bed to the required preheating temperature. The regeneration gas can advantageously be driven in a circle.

The exit temperature of the regeneration gas from the production bed varies with time within the phase. Typically, in the first half of the heating step, the exit temperature increase is less than 20%, preferably less than 10%, more preferably less than 5%, based on the difference between the preheat temperature and the initial temperature at the exit of the production zone at the beginning of the heating step.

In the second half of the heating step, the outlet temperature rises continuously. The difference between the outlet temperature at the end and at the beginning of the heating step is between 1% and 100%, preferably between 10% and 70%, more preferably between 20% and 50% of the difference between the preheat temperature and the initial temperature at the exit of the production zone at the beginning the heating step.

If the production bed contains a catalyst bed, advantageously in the regeneration phase, the catalyst bed can be freed from deposits which, for example, cause a reversible deactivation. This can be achieved by heating and optionally by adjusting a suitable atmosphere, eg water vapor content, to gasify coke deposits or, for example, oxygen to burn coke deposits. Advantageously, the heat-up step in the production bed and the heat-release step in the heat-recovery zone are synchronized, ie, both steps are started at the same time and last the same amount of heat in the regenerator bed gas supplied is between 0.5 and 2, preferably between 0.8 and 1.2.

Further steps:

Optionally, further steps may be integrated into the cycle, for example: (i) introducing fresh solid particles into the production bed and / or emptying the solid product from the production bed, (ii) discharging, exchanging the gas content of the reactor to avoid contamination of the product Avoid process gases in the individual steps. Step: Fill / empty solids

With regard to the solid particles in the production bed, the process can advantageously be carried out (quasi) continuously or batchwise.

In the quasi-continuous procedure advantageously within each cycle, a portion of the solid (solid product, spent contact, deactivated catalyst) withdrawn from the production bed and fresh solid (carrier, contact or catalyst) filled in the production bed, so that in the cyclically stationary operating state, the amount solids, composition and particle size distribution in the production bed are advantageously identical at the beginning of two consecutive cycles.

The filling and emptying of solid can advantageously be carried out either continuously or clocked.

In the batchwise procedure advantageously a solid is presented and over several cycles away neither refilled nor deducted. Advantageously, the batch time is between one cycle and 100,000 cycles, preferably between one cycle and 1,000 cycles, more preferably between one cycle and 100 cycles. After the batch time has elapsed, the solid (solid product, spent contact, deactivated catalyst) can be completely or partially emptied and fresh solid (carrier, contact or catalyst) introduced.

The relative duration for the filling / emptying of the solid, based on the duration of a full period, is advantageously between 0 and 100%, preferably between 0% and 50%, particularly preferably between 0% and 25%. Advantageously, the filling / emptying of the solids take place synchronously with the steps "hold" and / or "heat up" and / or "ejection" and / or "production" and / or "rinsing". Step: Extend

Advantageously, the extension of the gas holdup takes place in each cycle. The ejection step is optionally carried out at the beginning and / or at the end of the production phase. If the discharge takes place at the beginning of the production phase, the reactor is advantageously flowed through in the same flow direction as during the regeneration phase. If the discharge takes place at the end of the production phase, the reactor is advantageously flowed through in the same flow direction as during the production phase.

The gas in the feed may contain hydrogen, carbon monoxide, carbon dioxide, water vapor, nitrogen, argon or a mixture of these gases.

The feed temperature of the gas stream during the Ausschubschrittes is advantageously -150 to 750 ° C, preferably -75 to 600 ° C, more preferably 4 to 400 ° C, in particular 20 to 250 ° C.

During the discharge step, the gas stream advantageously has a flow rate in the production zone of 0.001 to 20 m / s, preferably from 0.01 to 10 m / s, more preferably from 0.05 to 5 m / s, in particular from 0.1 to 2 m / s. The volume of the gas introduced into the reactor during the discharge step is advantageously from 1 to 1000 times, preferably from 2 times to 100 times, more preferably from 5 to 10 times, the reactor volume. The gas volume corresponds to the volume at the inlet pressure and at the inlet temperature during the ejection step.

The relative duration of the Ausschubschrittes, based on the duration of a full period is advantageously between 0 and 10%.

The solid packing in the production zone can have different fluidization states analogous to the production step and the rinsing step during the ejection step, if it is flowed through in the same flow direction as during the production phase: advantageously a moving bed or a fluidized bed, preferably a fluidized bed.

If the solid packing is flowed through in the production zone during the discharge step in the same flow direction as during the regeneration phase, it can form a moving bed.

The ejection step advantageously proceeds in synchronism with the steps "storage" (same flow direction of the educt) or "release" (reverse flow direction of the educt). Keep pace

The holding step is optionally carried out at the beginning and / or at the end of the production phase. In this case, the flow through the production bed is advantageously interrupted by gas. The relative duration of the holding step, based on the duration of a full period, is advantageously between 0 and 50%, preferably between 0 and 10%.

Advantageously, the holding step takes place synchronously with the step "release" in the heat recovery zone and / or with the step "discharge / filling" in the production zone.

General details:

In the design of the cycles are advantageous u.a. following rules:

1 . The ratio between the heat capacity of the gases which flow through the production bed during the regeneration phase and the heat capacity of the gases which flow through the production bed during the production phase is advantageously between 0.5 and 2, preferably between 0.7 and 1.5 preferably between 0.9 and 1, 1.

2. The ratio of the heat capacities of the gas streams which flow through the reactor during the production step and during the purging step must correspond approximately to the following rule:

\ AT _ad \, where

Cprod ^ eff

C _purge | jJ: Heat capacity of the gas during the purge step

Fl: Heat capacity of the gas during the production step

X _e q [%] '■ At the required preheating temperature achievable equilibrium conversion of the educt during the production phase.

ΔΤ _β [K]: effective temperature elevation within the reaction zone. Ύ _{β {{} is the difference between the required preheat temperature and the onset temperature of the endothermic reaction.

\ ΔΤ _αά \ [K]: absolute value of the adiabatic temperature change of the endothermic reaction (for definition see http://elib.uni-stuttgart.de/bitstream/1 1682/2350/1 / docu_FU.pdf page

31).

The pressure in the reactor can optionally be varied during the individual phases of the cycles. The following variants are advantageous: (i) Production phase at high pressure of advantageously 2 to 60 bar, preferably 3 to 50 bar, particularly preferably 5 to 40 bar, in particular 10 to 30 bar, and regeneration phase at low pressure of advantageously ambient pressure to pressure of the production phase , In this case, we speak of a pressure swing mode. If the production phase and the regeneration phase have different pressures, the production gas and the regeneration gas are advantageously carried out in two separate cycles, (ii) production and regeneration phase at high pressure of advantageously 2 to 60 bar, preferably 3 to 50 bar, particularly preferred 5 to 40 bar, in particular 10 to 30 bar. In a pressure swing mode, the filling of the solid takes place (carrier, contact or catalyst) advantageous at low pressure, in particular from preferably 1 to 10 bar absolute, preferably 1 to 6 bar absolute, more preferably 1 to 4 bar absolute.

The reactor can advantageously be started from the cold state by feeding an inert gas, for example nitrogen or argon, to the reactor, periodically at intervals of from 1 minute to 100 minutes, preferably from 2 minutes to 50 minutes, more preferably from 5 minutes to 20 minutes Minutes the direction of flow through the reactor is reversed. At the same time, the heat input in the heating zone is advantageously activated. The start-up phase advantageously lasts between 1 and 100 cycles, preferably between 5 and 20 cycles. After this start-up phase, the process is switched over to the intended driving style.

reactor

The present invention further comprises a structured reactor containing three zones, a production zone containing a packing of solid particles, a heating zone and a heat recovery zone comprising a fixed bed, e.g. a random packing of moldings or a structured packing of monoliths or profiled sheets, wherein the pack of solid particles and the fixed bed consist of different materials and solid particles can be filled and discharged during the reactor operation. The heating zone may be located in the connection above the production and heat recovery zones (Figure 1). In this construction, the heating zone is directly accessible from above. Thereby, the required devices for the metering and distribution of the side stream during the heat introduction step can be installed over the one end of the reactor.

Between the heating zone and the heat recovery zone can advantageously be installed a hot gas filter, for example made of silicon carbide. In this filter, advantageously solid particles entrained with the product stream, e.g. Carbon particles, retained and burned or gassed. During the regeneration phase, the filter is advantageously backwashed, thereby ensuring its reliable function.

The production zone can be advantageously equipped with a monolith heat storage in addition to the random particle bed that forms the production bed. The ratio of the channel width of the monoliths to the particle size of the particles is advantageously between 10 and 100, preferably between 20 and 50. The monoliths may advantageously consist of temperature-resistant ceramic or of carbon. The monoliths can advantageously fill the production zone over the entire length or in zones. The channel width of the monoliths is advantageously between 2 to 100 mm, preferably 5 to 50 mm. The production zone, the heating zone and the heat recovery zone can advantageously be arranged vertically in a line (FIG. 2). dimensioning

The reactor according to the invention can be designed, for example, as a shaft reactor. Each shaft advantageously has a length of 0.5m to 50m, preferably from 1m to 20m, more preferably from 2m to 20m. The flow cross section of the shafts is advantageously between 0.0005m ² and 100m ² , preferably between 0.005m ² and 50m ² . The production bed advantageously occupies more than 50%, preferably more than 70% of the total height of the shaft in the production zone. The regenerator bed occupies more than 50%, preferably more than 70%, of the total height of the well in the heat recovery zone.

The shaft reactor is advantageously lined fireproof and thermally insulated.

The table shows the performance characteristics of different process variants for the case of methane pyrolysis. This leads to specific advantages and disadvantages.

Modes of operation:

The reactor according to the invention can advantageously be operated in a two-step operation with hot gas feed (FIG. 3b):

Production phase regeneration phase

1 . Step 2. Step

Production bed production heating up

Heating zone heat input idle

Regenerator bed storage release The term "two-step operation" refers to the number of steps in the production phase within a cycle, with the steps of dumping, holding, and filling and draining solids not being taken into account In the first step, production advantageously takes place in the production bed while in parallel in the heating zone In the second step, the heating takes place advantageously in the production bed, while the release takes place in the regenerator bed.The advantages and disadvantages of the two-step operation are abbreviated as follows:

+ Simple configuration for carrying out the method according to the invention,

o Moderate temperature gradients.

No complete heat recovery feasible.

A gaseous heat transfer medium heated to the level of the preheating temperature must be fed into the heating zone with twice to five times the volume flow of the reactant stream.

- Dilution of the product stream through the gaseous heat transfer medium.

Alternatively, the reactor according to the invention can advantageously be operated in three-step operation with heat generation in the heating zone (FIG. 4b and FIG. 5b):

The term "three-step operation" refers to the number of steps in the production zone within a cycle, with the steps of dumping, holding and filling and dumping solids not taken into account.

In the first step, production advantageously takes place in the production bed, while storage takes place in the regenerator bed. In the second step, the rinsing takes place advantageously in the production bed, while in the heating zone a heat input takes place and storage takes place in the regenerator bed. In the third step, the heating advantageously takes place in the production bed, while the release takes place in the regenerator bed.

Advantages and disadvantages:

+ Simple configuration for carrying out the method according to the invention.

+ A complete heat recovery feasible.

+ The product stream can be recovered at high concentration / purity without dilution by gas from the rinse step. o Elaborate process control: three steps per cycle.

The different gas flow rates in the three steps complicate the fluidic dimensioning of the reactor.

Temperature gradients in the vicinity of the heating zone.

Variants of the reactor structure

In the production zone heaters can be installed advantageously. These devices may be, for example, gas-fired radiant tubes, electric heaters and / or electrodes that conduct electrical current through the solid packing. Furthermore, heating surfaces can advantageously be installed in the regenerator bed.

Alternatively, multiple side feeds can be installed along the heat recovery zone. This variant is shown in FIG. The number of page feeds is advantageously determined according to the following rule:

n _inj = l + int ^■ \ AT _aa, wherein

Number of page feeds

int: function: integer part of a real number

X _eq [%] '■ At the required preheating temperature achievable equilibrium conversion of the educt during the production phase.

& T _e ff [K]: effective temperature elevation within the reaction zone. AT _ef f corresponds to the difference between the required preheat temperature and the onset temperature of the endothermic reaction. \ ΔΤ _αα \ [K]: absolute value of the adiabatic temperature change of the endothermic reaction (for definition, see http://elib.uni-stuttgart.de/bitstream/1 1682/2350/1 / docu_FU.pdf page 31). Determining the position of the feeds is governed by a length scale, which can be clearly described as the "migration interval of a thermal front." The migration interval of a thermal front is determined according to the following rule:

c _fxb [j - ^ -]: specific heat capacity of the solid _packing in the heat recovery zone.

The positions of the side feeds are advantageously determined according to the following rules: (i) the distance of the first side feed from the upper end of the heat return zone corresponds favorably to the thermal front migration interval during the storage step, (ii) the distance between successive side feeds advantageously corresponds to the migration interval of thermal front during the storage step. This variant of the reactor according to the invention can advantageously be operated in two-step operation with heat generation in the heating zone (FIG. 6b):

Advantages and disadvantages:

+ Complete use of the heat capacity of the regenerator bed with moderate gas flows possible.

o Relatively low contamination / dilution of the product stream by the combustion gases from the heat input.

Embedding of one or more heating zones in the regenerator bed is constructive and material technically complex.

No complete heat recovery feasible.

Temperature gradients in the vicinity of the heating zones.

Advantageously, the reactor according to the invention can also be equipped with two production beds (FIG. 7). The production beds are advantageously connected to the top of the regenerator bed. Advantageously, each of the two production beds can be switched separately to a supply or discharge in the periphery of the process. The streams from the two production beds are advantageously combined at the entrance to the heating zone. The gas temperature at the inlet to the heating zone is advantageously between the onset temperature of the endothermic reaction and the required preheating temperature.

The reactor according to the invention can advantageously be operated in four-step operation with heat generation in the heating zone (FIG. 7b):

The term "four-step operation" refers to the number of steps in the production zone within one cycle, excluding the ejection steps. In the first step, production advantageously takes place in the first production bed, while rinsing takes place in the second production bed. In parallel, the heat input takes place in the heating zone and storage in the regenerator bed.

In the second step, the holding takes place advantageously in the first production bed, while the heating takes place in the second production bed. At the same time, the release takes place in the regenerator bed.

In the third step, rinsing advantageously takes place in the first production bed, while production takes place in the second production bed. In parallel, the heat input takes place in the heating zone and storage in the regenerator bed.

In the fourth step, the heating takes place advantageously in the first production bed, while holding takes place in the second production bed. At the same time, the release takes place in the regenerator bed.

Advantages and disadvantages:

+ A complete heat recovery feasible.

+ Holding step without flow through the production bed can be used for filling and emptying of solid,

o Moderate temperature gradients.

Elaborate process control: four steps per cycle.

Costly in terms of equipment: Three tanks and the corresponding periphery (metering and shut-off devices for gas and solid) required in one reactor. Combination of several reactors

The cyclical driving requires a discontinuous production. In order to achieve continuous production, advantageously two or more reactors according to the invention can be connected in parallel. Advantageously, the production step is carried out in at least one reactor.

With parallel connection of two reactors according to the invention, each with a production bed, a heating zone and a regenerator bed in two-step operation, the following steps advantageously take place (FIG. 3c and FIG. 6c):

1 . Step 2. Step

Production bed production heating up

1st reactor heating zone heat input

Regenerator bed storage release

Production bed heating production

2nd reactor heating zone heat input

Regenerator bed release storage the steps of pouring, holding and filling solids and discharging are not taken into account.

In the first step, production advantageously takes place in the production bed of the first reactor, while in the heating zone of the first reactor the heat input takes place and in the regenerator bed of the first reactor storage takes place. In parallel, in the second reactor, the heating takes place advantageously in the production bed, while the heat release takes place in the regenerator bed of the second reactor.

In the second step, the heating advantageously takes place in the production bed of the first reactor, while the release takes place in the regenerator bed of the first reactor. Parallel to this, in the second reactor, production advantageously takes place in the production bed, while in the heating zone of the second reactor the heat input takes place and in the regenerator bed of the second reactor the release takes place. With parallel connection of two reactors according to the invention, each with a production bed, a heating zone and a regenerator bed in three-step operation, the following steps advantageously take place (see FIG. 4c):

the steps of pouring, holding and filling solids and discharging are not taken into account.

In the first step, production advantageously takes place in the production bed of the first reactor, while storage takes place in the regenerator bed of the first reactor. At the same time, rinsing takes place in the second reactor, advantageously in the production bed, while the heat input takes place in the heating zone and storage takes place in the regenerator bed of the second reactor.

In the second step, production advantageously takes place in the production bed of the first reactor, while storage takes place in the regenerator bed of the first reactor. In parallel, heating takes place in the second reactor, advantageously in the production bed, while the release takes place in the regenerator bed of the second reactor.

In the third step, rinsing advantageously takes place in the production bed of the first reactor, while in the heating zone the heat input takes place and in the regenerator bed of the first reactor. actors storage takes place. Parallel to this, in the second reactor, production advantageously takes place in the production bed, while storage takes place in the regenerator bed of the second reactor.

In the fourth phase, the heating takes place advantageously in the production bed of the first reactor, while the release takes place in the regenerator bed of the first reactor. Parallel to this, in the second reactor, production advantageously takes place in the production bed, while storage takes place in the regenerator bed of the second reactor.

With parallel connection of three reactors according to the invention, each with a production bed, a heating zone and a regenerator bed in three-step operation, the following steps advantageously take place (see FIG. 5c):

In the first step, production advantageously takes place in the production bed of the first reactor, while storage takes place in the regenerator bed of the first reactor. In parallel, the rinsing takes place in the second reactor advantageously in the production bed, while in the heating zone, the heat input takes place and storage takes place in the regenerator bed of the second reactor. At the same time, heating takes place in the third reactor, advantageously in the production bed, while the release takes place in the regenerator bed of the third reactor.

In the second step, the rinsing advantageously takes place in the production bed of the first reactor, while the heat input takes place in the heating zone and the storage takes place in the regenerator bed of the first reactor. In parallel, in the second reactor, the heating advantageously takes place in the production bed, while the release takes place in the regenerator bed of the second reactor. Parallel to this, in the third reactor, production takes place advantageously in the production bed, while storage takes place in the regenerator bed of the third reactor. In the third step, the heating takes place advantageously in the production bed of the first reactor, while the release takes place in the regenerator bed of the first reactor. Parallel to this, in the second reactor, production takes place in the production bed, while in the regeneration Rator bed of the second reactor storage takes place. In parallel, in the third reactor, the rinsing takes place advantageously in the production bed, while in the heating zone the heat input takes place and storage takes place in the regenerator bed of the third reactor.

With parallel connection of two reactors according to the invention, each with two production beds, a heating zone and a regenerator bed in four-step operation, the following steps advantageously take place (see FIG. 7c):

wherein the Ausschubschritte are not taken into account.

In the first step, advantageously in the first production bed of the first reactor, the production and in the second production bed of the first reactor rinsing takes place while in the heating zone of the first reactor, the heat input takes place and storage takes place in the regenerator bed of the first reactor. In parallel, in the second reactor, advantageously in the first production bed, the heating takes place and in the second production bed of the second reactor of the holding step, while in the regenerator bed of the second reactor, the release takes place.

In the second step, advantageously, the heating step takes place in the first production bed of the first reactor and the heating in the second production bed of the first reactor, while the release takes place in the regenerator bed of the first reactor. In parallel, in the second reactor, the production advantageously takes place in the first production bed and the rinsing takes place in the second production bed of the second reactor, while storage takes place in the heating zone of the second reactor and in the regenerator bed of the second reactor.

In the third step, advantageously in the first production bed of the first reactor, the rinsing and in the second production bed of the first reactor, the production takes place while in the heating zone of the first reactor, the heat input takes place and the storage takes place in the regenerator bed of the first reactor. Parallel to this, in the second reactor, advantageously takes place in the first Production bed of the holding step and in the second production bed of the second reactor, the heating takes place while in the regenerator bed of the second reactor, the release takes place. In the fourth step, advantageously in the first production bed of the first reactor, the heating takes place and in the second production bed of the first reactor of the holding step, while in the re-generator bed of the first reactor, the release takes place. Parallel to this, in the second reactor, the rinsing takes place advantageously in the first production bed and the production in the second production bed of the second reactor, while in the heating zone of the second reactor the heat input takes place and storage takes place in the regenerator bed of the second reactor.

advantages

The present invention solves the following feasibility problems of previously considered methane pyrolysis reactor concepts, i. (i) fouling the heating surfaces by indirect heating coke deposits; (ii) forcibly coupling the solid particle flow to the requirements of heat integration and / or thermal power; (iii) heat loss due to unequal adjustment of the heat capacity flows between the production phase and the regeneration phase and consequently asynchronous temperature fronts (v ) Loss of yield due to the reverse reaction of hydrogen during cooling in the heat recovery zone, (vi) handling of hot solids and (vii) contamination by combustion fumes.

Further, the present invention mitigates the largest cost drivers (see the following estimate) of the concepts considered in the prior art by (i) eliminating the need for heat transfer walls in the region of the production zone, (ii) the solids sluices for feeding the solid particle stream into the reactor can be designed without pressure and (iii) the process offers complete heat integration.

The required process heat is generated in the present invention by combustion in the heating zone of the reactor. The elaborate heat transfer surfaces for indirect coupling of the process heat at high temperature omitted. Thus, the flow of solids passing through the reactor is no longer rigidly coupled to the requirements of heat integration. In particular, the solids flow may just correspond to the production rate of the solid product, so that the hold-up of the production zone remains constant. The gaseous product stream is separated from the carbon at the highest temperature level, thus yield losses due to a reverse reaction are excluded.

The reactor can be designed as a shaft apparatus (with one, two or three shafts) without any structuring of the cross section. The simple geometry allows the reactor chamber to be refractory lined and thermally insulated. Thus, the pressure-bearing reactor shell can be effectively protected from the high temperatures of the reaction media.

Due to the optional installation of several heat sources in the heating zone, for example burners, plasma generators or resistance heaters, the concept according to the invention offers the possibility of switching between different energy sources in a flexible and cost-optimized manner. Thus, a hybrid heating of the process can be realized, as described for example in WO 2014/090914. Estimation of the costs:

^* : Savings potential

(i) versus indirect heating methods: by eliminating heat transfer walls in the high temperature range

(ii) versus electric heating methods: no need for electrodes / electrical resistors in the high temperature range

* ^* : Potential savings compared to fluidized bed processes:

By the reaction in the resting bed, the soot formation is suppressed. The regenerator bed functions as a regenerable filter for dust particles. This can be dispensed with an external filtration stage.

* ^** : The cyclic method has two advantages:

(i) The loading and unloading of the reactor can be carried out on a non-flow-through bed.

(ii) Optionally, the cyclic process can be operated in pressure swing mode: high pressure production and low pressure regeneration. In this case, the pressure balance in the solids locks can be omitted.

(iii) The flow of solids passing through the production zone is approximately 30% of the solids flow required in moving bed reactors, where heat recovery is controlled by the flow of heat

Countercurrent flow between the gaseous and the solid process stream based.

Figures Designations of Figures 1 and 2:

1: production bed

2: regenerator bed

3: heating zone

4: mixing / combustion chamber

5: filling the carrier

6: emptying the solid product

7: Hot gas filter

8: Additional heating in the production bed

9: Additional heating in the regenerator bed

10: Phase separator / dedusting Figure 1 shows a schematic representation of the reactor according to the invention with a production and a regenerator bed in a parallel arrangement.

FIG. 2 shows a schematic representation of the reactor according to the invention with a production bed and a regenerator bed in a vertical arrangement.

Designations of FIG. 3:

1: production bed

2: regenerator bed

3: heating zone

4: mixing / combustion chamber

5: filling the carrier

6: emptying the solid product

7: Hydrocarbon-containing feed stream

8. Product gas exit stream

9: regeneration gas outlet flow

10: Regeneration gas feed stream

13: Oxygen-containing feed stream

14: Fuel-side feed stream

Figure 3a shows a schematic representation of the method according to the invention with two identical reactors, each with a production bed, a heating zone and a regenerator, wherein the heat input is accomplished by combustion of a fuel in an external combustion chamber.

FIG. 3b shows the flow chart in the process according to the invention over a cycle with two main steps in the production bed.

FIG. 3c shows the flow chart of a quasi-continuous production in the process according to the invention in a configuration with two identical reactors. Designations of FIG. 4:

1: production bed

2: regenerator bed

3: heating zone

4: page feed

5: filling the carrier

6: discharging the solid product

7: Hydrocarbon-containing feed stream

8. Product gas exit stream

9: regeneration gas outlet flow

10: Regeneration gas feed stream

1 1: purge gas feed stream

12: purge gas exit stream 13: Oxygen-containing feed stream

FIG. 4a shows a schematic representation of the method according to the invention with two identical reactors, each with a production bed, a heating zone and a regenerator bed, wherein the heat input is accomplished by side feeding of an oxidizer into the heating zone.

FIG. 4b shows the flow chart in the process according to the invention over a cycle with three main steps in the production bed.

FIG. 4c shows the flow chart of a quasi-continuous production in the process according to the invention in a configuration with two identical reactors.

Designations of FIG. 5:

1: production bed

2: regenerator bed

3: heating zone

4: page feed

5: filling the carrier

6: discharging the solid product

7: Hydrocarbon-containing feed stream

8. Product gas exit stream

9: regeneration gas outlet flow

10: Regeneration gas feed stream

1 1: purge gas feed stream

12: purge gas exit stream

13: Oxygen-containing feed stream

FIG. 5a shows a schematic representation of the method according to the invention with three identical reactors, each with a production bed, a heating zone and a regenerator bed, the heat input being brought about by lateral feeding of an oxidizer into the heating zone.

FIG. 5b shows the flow chart in the invention over a cycle with three main steps in the production bed.

FIG. 5c shows the flow chart of a quasi-continuous production in the process according to the invention in a configuration with three identical reactors.

Designations of FIG. 6:

1: production bed

2: regenerator bed

3: heating zone

4: mixing / combustion chamber

5: filling the carrier

6: emptying the solid product 7: Hydrocarbon-containing feed stream

8. Product gas exit stream

9: regeneration gas outlet flow

10: Regeneration gas feed stream

13: Oxygen-containing feed stream

14: Fuel-side feed stream

Figure 6a shows a schematic representation of the inventive method with two identical reactors, each with a production bed, a heating zone and a Regenerator- bed, wherein the heating zone integrated in the heat recovery zone and the heat input by combustion of a fuel in an external combustion chamber or by side feed of an oxidizer can be accomplished in the heating zone.

FIG. 6b shows the flow chart in the process according to the invention over a cycle with two main steps in the production bed.

FIG. 6c shows the flow chart of a quasi-continuous production in the process according to the invention in a configuration with two identical reactors.

Designations of FIG. 7:

1 a: production bed 1

1 b: production bed 2

2: regenerator bed

3: heating zone

4: page feed

5: filling the carrier

6: emptying the solid product

7: Hydrocarbon-containing

feed stream

8. Product gas exit stream

9: regeneration gas outlet flow

10: Regeneration gas feed stream

1 1: purge gas feed stream

13: Oxygen-containing feed stream

FIG. 7a shows a schematic representation of the method according to the invention with two identical reactors, each with two production beds, a heating zone and a regenerator bed, wherein the heat input is accomplished by side feeding of an oxidizer into the heating zone. In this configuration, two identical reactors are required for continuous production.

FIG. 7b shows the flow chart in the process according to the invention over a cycle with three main steps in the production beds. FIG. 7c shows the flow chart of a quasi-continuous production in the process according to the invention in a configuration with two identical reactors.

FIG. 8 shows, by way of example, the process flow diagram of an integrated, quasi-continuous process according to the invention. In this process, natural gas (strand 3) and air (strand 1) are introduced as gaseous feed streams. The natural gas is the starting material for the production of the target products hydrogen and pyrolysis carbon. The air is split into two partial streams. A partial flow (strand 4) is rich in oxygen and is passed as an oxidizer in the heating zone. The second partial flow is nitrogen rich and is used as the main flow during the regeneration phase (strand 7) and as purge gas for the buffer, receiver and discharge (strand 9, strand 1 1) for the solid process streams. The process includes three reactors that are cycled. Only the active lines are shown. In reactor R1, the production bed is in the production step, the heating zone is idle and the regenerator bed is in the step «store heat». The buffer tank for the solid support B1 1 is filled. The discharge container B13 is relaxed. In reactor R2, the production bed is located in the step "Rinsing", the heating zone in the step "Heat input" and the regenerator bed in the step "Heat storage". The buffer tank B21 is pressurized with nitrogen to the level of the process pressure, and the solid support is transferred from the buffer tank B21 to the receiver tank B22. The discharge container B23 is emptied. In the reactor R3, the production bed is in the «Heating up» step, the heating zone is idling and the regenerator bed is in the

Step "Release heat". The buffer tank B31 is relaxed. The solid support is filled from the feed tank B32 into the production zone of the reactor R3. At the same time, the solid reaction product from the production zone of the reactor R3 is transferred to the discharge tank B33. The following process steps are included in the periphery of the reactors: In the air separation stage, the supply air is separated into an oxygen-rich and a nitrogen-rich fraction. In the gas separation stage, the gaseous crude product is separated into a hydrogen-rich product stream and into a retentate stream. The retentate is returned to the process as the main stream for the purge step. The gas from the rinsing step is partially dried in a condenser and returned to the process. The nitrogen-rich stream is at the level of the process pressure (strand 1 1 and strand 12) and available as purge gas for pressure equalization with the environment (strand 9 and strand 10). The process is designed for an annual production capacity of 720000 Nm ^{3 of} hydrogen. The production bed and the regenerator bed have a cross-section of 44m ² and a bed height of 6m. The production bed is filled with a carbon carrier with a mean grain size of 3 mm and a bulk density of 800 kg / m ³ . The regenerator bed consists of particles of alumina with a mean grain size of 3mm. The process pressure of the feed streams is 10 bar _a bs- The feed temperature of the feed streams is 200 ° C. The preheating temperature is 1800 ° C. The cycle time is 5400s. Within one cycle, the production step, the rinsing step and the heating step each take 1800s. The current bar shows in tabular form the averaged over the duration of a step currents in the individual strands. example

power strip

Mole flows [kmol / h]

electricity

C CH4 CO CO2 H2 H20 N2 02

1 0 0 0 0 0 0 1602 400

2 0 23 0 0 4455 0 133 0

3 0 2250 0 0 0 0 133 0

4 0 0 0 0 0 0 128 400

5 0 23 45 1 755 6 6633 0

6 0 0 57 11 33 774 6761 0

7 0 0 0 0 0 0 11207 0

8 0 0 0 0 0 0 11207 0

9 0 0 0 0 0 0 11207 0

10 0 0 0 0 0 0 11207 0

11 0 0 0 0 0 0 11207 0

12 0 0 0 0 0 0 11207 0

13 1125 0 0 0 0 0 0 0

14 3353 0 0 0 0 0 0 0

Claims

claims

1. A method for carrying out endothermic gas phase or gas-solid reactions, characterized in that in a production phase in a first reactor zone, the production zone which is at least partially filled with solid particles, wherein the solid particles in the form of a fixed bed, a moving bed and sections or in the form of a fluidized bed, the endothermic reaction is carried out and the product-containing gas stream in the range of the highest temperature level plus or minus 200 K is withdrawn from the production zone and the product-containing gas stream through a second reactor zone, the heat recovery zone, at least partially Fixed bed contains, is stored, wherein the heat of the product-containing gas stream is stored in a fixed bed, and in the subsequent rinsing step, a purge gas is passed in the same flow direction through the production zone and the heat recovery zone, and in a heating zone between the Prod the heat required for the endothermic reaction in the product-containing gas stream and in the purge stream or in the purge stream, and then in a regeneration phase, a gas flows in the reverse flow direction through the two reactor zones and heats the production zone.

2. The method according to claim 1, characterized in that the heat required for the endothermic reaction is introduced into the purge stream.

3. The method according to claim 1 or 2, characterized in that during the regeneration phase, a possible heat input in the heating zone with a related to the volume of the heating zone heat output is less than 100kW / m ³ .

4. The method according to at least one of claims 1 to 3, characterized in that the averaged over a period sinking rate of the solids flow in the production zone in the range of 0 m / h to 50 m / h.

5. The method according to at least one of claims 1 to 4, characterized in that the specific interface between the solid particles in the production zone and the gas phase and / or the fixed bed in the heat recovery zone and the gas phase is greater than 50 m2 / m3.

6. The method according to at least one of claims 1 to 5, characterized in that the solid particles of the production zone are a catalyst for an endothermic gas phase reaction, a solid contact for an endothermic gas-solid reaction and / or the product of an endothermic reaction and that the fixed bed the heat recovery zone is chemically inert with respect to the reverse reaction of the endothermic reaction.

Method according to at least one of claims 1 to 6, characterized in that the ratio between the heat capacity of the gases which flow through the production bed during the regeneration phase and the heat capacity of the gases which flow through the production bed during the production phase is between 0.5 and 2 lies.

Method according to at least one of claims 1 to 7, characterized in that the heat required for the endothermic reaction is introduced by combustion of a fuel gas with the aid of an oxygen-rich gas in the heating zone, wherein the fuel gas in the main stream from the production zone during the production step or during the Flushing step is included and the fuel gas has temperatures of 350 ° C to 1200 ° C when entering the heating zone.

Method according to at least one of claims 1 to 8, characterized in that the process is operated cyclically and the production phase occupies between 20 and 60% of the period and the regeneration phase between 20 and 60% of the period, wherein the rinsing step between 0 and 40% of Takes period.

10. The method according to at least one of claims 1 to 9, characterized in that the loading and unloading takes place in the production zone with solid particles, while the production zone is not flowed through with edukthaltigem gas.

1 1. The method according to at least one of claims 1 to 10, characterized in that the method is operated in the pressure change mode, wherein the production phase is carried out at a pressure in the range of 2 to 60 bar and the regeneration phase at a pressure in the range 1 to 10th bar is performed.

12. The method according to at least one of claims 1 to 10, characterized in that the educt-containing stream has a flow rate in the production zone of 0.001 to 20 m / s.

13. The method according to at least one of claims 1 to 12, characterized in that are carried out as endothermic gas phase or gas-solid reactions, the following processes: Preparation of hydrogen, of synthesis gas, of styrene, propene, butene and / or benzene, from Acetylene, carbon monoxide, hydrogen cyanide and the calcination of aluminum hydroxide.

14. The method according to at least one of claims 1 to 13, comprising the method steps (a) introducing a edukthaltigen gas in a preheated production zone and performing the endothermic reaction in the production zone, which is at least partially filled with solid particles (process step: production), (b ) optionally heat input to the product-containing gas stream in a heating zone, which is arranged downstream of the production zone (process step: heat input), (c) heat transfer from the product-containing Stream from step (b) to a packing of solid particles and / or structured internals in a heat recovery zone located downstream of the heating zone (process step: heat storage), (d) purging the production zone and the heat recovery zone with an inert purge gas in the direction of flow of the educt-containing gas (Process step purging), (e) heat input to the product-containing gas stream in a heating zone, which is located downstream of the production zone (process step: heat input), (f) interrupting the introduction of edukthaltigem gas and introducing a regeneration gas in the heat recovery zone with compared to edukthaltigen gas (b) heat transfer from the solid particles heated in step (c) and / or structured internals to the regeneration gas (process step: heat release), (h) heat transfer from the regeneration gas heated in step (e) to the solid particles l in the production zone (process step: heating), (i) interrupting the introduction of regeneration gas in the heat recovery zone and introducing a edukthaltigen gas in a preheated production zone with compared to the regeneration gas flow direction analogous step (a).

Reactor comprising three zones, a production zone containing a packing of solid particles, a heating zone and a heat recovery zone comprising a fixed bed, wherein the solid particle packing and the fixed bed are made of different materials and solid particles can be filled and discharged during reactor operation.